Orthodihydroxy azo dyestuffs



Patented Sept. 2, 1941 UNITED sures PATENT- orrica QRTHODIHYDBOXY AZO DYESTUFFS Richard Fleischhauer, Frankfort-on-the-Main- Fechenneim, Paul Zervas, Cologne-Muhlheim, and Adolf Miiller, Frankfort-on-the-Main- Fechenheim, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application February 3, 1940, Serial No. 317,123. In Germany February18, 1939 4 Claims.

Our present invention relates to ortho-hydroxy azodyestufis more particularly to those of the general formula:

components of the general formula:

IH-x-z no I i wherein X, Y and Zhave the aforesaid signification.

The new dyestuffs yield when chromed on the fiber by the afterchrome or meta-chrome process valuable grey shades distinguished in compari' son with known analogous dyestufis byasuperior fastness particularly to fulling and potting.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in degrees centigrade.

Example 1 The diazo solution of 14.4 parts of 4-chloro-2- aminophenol is added to a cold solution of 34.3 parts of l-(benzoylamino)-7-hydroxynaph*thalene-B -sulfonic acid, containing an excess of sodium carbonate. After some hours the rombination is complete and the dyestuff formed is isolated. It is when dry a blue powder soluble in concentrated sulfuric acid with a violet color.

It dyes wool when afterchromed bright bluish grey shades of very good fastness'to light, fulling and potting and corresponds with the formula:

When combining in a like manner the diazccompound of 17.8 parts of 4.6-dich10ro-2-aminophenol with 42 parts 1-(25'-dichlorobenzoylamino) -7-hydroxynaphtha1ene-3-sulfonic a c i d in the presence of an excess of sodium carbonate the formed dyestuff of the formula:

is when dry a dark powdersoluble in a sodium carbonate solution with a violet and in concentrated sulfuric'acid with a violet-red color and dyes wool claret like red shades turning when afterchromed to a greenish gray of very good fastnessto light, fulling and potting,

Example '2 The diazocom-pound of 16.8 partsof 6-nitr'o-lmethyl-2-aminophenol is combined with 34.3 parts of l-benzoylamino-7-hydroxynaphthalene- B-sulfonic acid in the presence of an excess of sodium carbonate. The formed dyestufi of the formula:

v no out on I SOeH is when dry a chocolate like brown powder soluble in concentrated sulfuric acid with a bluish red color and dyes wool when flafterchromed fast bluish gray shades. 1

When combining the same diazocompound with 1-monochlorobenzoylarninoor l-dichlorobenzoylamino-7hydroxynaphthalene-3- or -lsulfonio acidstheformed dyestuffs dye wool when afterchromed similar fast bluish gray shades.

Example 3 The diazocompound of 15.4 parts of -nitro- 2-aminophenol is combined in the presence of an excess of sodium carbonate with 39.3 parts of 1- (4-toluenesulfonylamino) -'7-hydroxynaphthalene-3-sulfonic acid. The formed dyestuif of the formula:

is when dry a dark blue powder soluble in concentrated sulfuric acid with a reddish violet color and dyes wool when afterchromed bright greenish gray shades of very good fastness properties.

When using as coupling component the l-benzenesulfonyl aminoor 1 (4' chlorobenzenesulfonylaminoor 1 (3'4 dichlorobehzenesulfonylamino-) or 1-(2'5'-dimethyl-4' ch1orobenzenesulfonylamino) -7-hydroxynapthalene 3- or --4-sulfonic acid or as diazocomponent the 5 nitro 4 chloro-Z-diazophenol dyestuffs are obtained which dye Wool when afterchromed similar greenish gray shades of very good fastness properties. 7

Example 4 17.8 parts of 4.6-dichloro-2-aminophenol are diazotized in the usual manner and the diazocompound is salted out and filtered off. The paste thus obtained is added to a solution containing an excess of sodium carbonate and 31.9

parts of l-(n-butyrylamino) -7-hydroxynaphthalene-3-sulfonic acid. When thecom'bination has been finished the formed dyestufi of the formula:

NH-CO-CHPCHr-CH: N=

SOsH

is isolated.

It is when dry a blue powder, soluble in a sodium carbonate solution with a reddishblue color, in dilute acids witha red and in concentrated sulfuric-acid witha bluish red color and dyes wool from an acetic acid bath violet shades turning when after-chromed to a bluish gray of very good fastness properties.

Example 5.

The diazosuspension obtained by starting from 14.4 parts of 4-chloro-2-aminophenol is added to a solution of 35.1 of l-(n-butoxyacetyl)amino-L- hydroxynaphthalene-3-sulfonic acid containing an excess of sodium carbonate. When the combination has been finished the formed dyestuff of the formula: V

is isolated. It is when a dry'violet powder soluble in a sodium carbonate solution with a bluish red color, in concentrated sulfuric acid with a reddish violet color and dyes wool claret like shades turning when afterchromed to a bluish gray of a very good f astness particularly to fulling and potting v When combining the diazocompound of 4.6- dichloro-2-aminophenol with l-phenoxyacetylamino-7-hydroxynaphthalene-3-sulfonic acid in the presence of an excess of sodium carbonate the formed dyestuif of the formula:

Example 6 The combination of the diazocompound of 14.4 parts of S-chIoro-Z-aminophenol with 36.3 parts of 1 (cyclohexylacetyl) -amino-7-hydroxynaphthalene-3-sulfonic acid in the presence of an excess of sodium carbonate yields a dyestuii of the formula: v

' V H: H2

which is when dry a violet powder soluble in a sodium carbonate solution with a reddish blue color, in dilute acids with a red color and dyes wool dark red shades turning to a reddish bluegray of very good fastness, particularly to fulling, P tting and light.

When combining in a similar manner 4-chloro- 2 diazophenol with 1 (cyclohexylpropionyl) amino 7 -hydroxynaphthalene 3-sulfonic acid the formed dyestuif of the formula:

is soluble in concentrated sulfuric acid with a bluish red color and dyes wool claret like red shades turning when afterchromed to a gray of a very good fastness particularly to light, fulling and potting.

-Further dyestuffs obtainable according to the present invention are indicated in the following table:

when afterchromed to a greenish gray of very good fastness to light, fulling and potting.

Coloration of the solution of the formed dyestufi inthade of {lhe yelngw en Diazocomponent Coupling component aftemhmmed Concentrated Sodium caron wool sulfuric acid bonate solution 4.6-dichloro-2-aminophenol l-(igigminobegzoyl)-amino-7-hydroxynaphthalene-3- Bluish red Violet Greenish gray.

s omc aci D 1-(4-aminobenzoyl)-amino-7-hydroxynaphthalene-3- do do Do.

sulfonic acid. l-(phenoxyacetyl-amino)-7-hydroxynaphthalene-4- do Reddishblue. Gray.

sulfonic acid. l-hexahydrobenzoylamino-7-hydroxynaphthalene-3- Claret like red Greenish gray.

sulfonic acid. 1-(cyclohexylacetyl)-ammo 7-hydroxynaphthalin-El- Bluish red- Gray.

sulfonic acid. 1-(phenylacetyl)amino-7-hydroxynaphtha1ene-4- do Bluish violet Reddish gray.

sulfonic acid. l-f(n-putyriylamino)-7hydroxynaphthalene 8-su1- Red Reddish blue Do.

omc aci 1-(3-aminobenzoyl-amino)-7-hydroxynaphthalene- .do do Do.

3-sulfonic acid. 7 1-(begzoylamino)-7-hydroxy-naphthalene-B-sulfonic do do Do.

an 1-(cyclohexylpropionyl)-amino-7-hydroxy-naphdo do Do.

thalene-S-sulfonic acid. 1-(3-nitrobenroylamino)-7-hydr0Xy-Ilaphthalenedo Violet Bluishblack.

3-sulfonic acid. 1-(4-nitrobenzoyl-a1mno)-7-hydroxy-naphthalenedo Bluishviolet. Do.

3-sulionic acid. 4-methyl-6-nitro-2-aminopheno1. l-zgn-l ititoryacegyl-ammo)-7-hydroxy-naphthalene- B1uishred Blue Gray.

-su omc acl Do 1-(phenoxyacetyl-amino)-7-hydroxy-naphthalenedo do Do,

3- sulfonic acid. 4-nitm-2-aminophenol 1- (n-puto i3yacety1-ammo)-7-oxynaphthalene-3-sul- Red Reddishviolet Olive.

omc aci 4-chloro-6-nitro-2-a1ninophenol n Bluish red Blue ueay- 6-chloro-4-nitro-2-aminophenol l-(ilil-llgutoxyargtyl-ammo)-7-hydroxynaphthalene-3 Red Bluish red Olive-gray.

s omc aci 4.6-dichloro-2-amino-phenol o Bluish red Violet Gray.

Do l-( ilfiutpxyagetyl-ammo)-7-hydroxynaphthalene-4- o-- Reddish blue Beddish gray.

s omc B01 We claim: 1. Ortho-dihydroxy azodyestufis of the general formula:

SOQH

which is when dry 2, dark powder soluble in a sodium carbonate solution with a violet'and in concentrated sulfuric acid witha violet-red color and. dyes wool claret like red shades turning 3. I he orthodihydroxy azodyestufi' of the formula:

which is when dry a watersoluble powder, soluble in concentrated sulfuric acid With a bluish red 100101 and dyes wool violet shades turning when afterchromed to a bluish gray of a very good fastness to light, fulling and potting.

4. The orthodihydroxy azodyestufi of the forwhich is soluble in concentrated sulfuric acid with a bluish red color and dyes wool claret like red shades turning when afterchromed to a gray of a very good fastness particularly to light, fulling and'potting.

RICHARD FLEISC'I-II-IAUER. PAUL ZERVAS. ADOLF 

